Living anionic polymerization using the conjugated rod macroinitiator was extensively employed to obtain well-defined block copolymers as shown in Scheme 3(c). Francois et al. reported the synthesis of poly(p-phenylene)-b-polystyrene (PPP-b-PS) or PPP-b-PMMA copolymers via the combination of living anionic polymerization followed by the aromatization of poly(1,3-cyclohexadiene) moiety [76] and [77]. Our group prepared PF-b-P2VP diblock copolymers from the vinyl end-functionalized PF macroinitiator [25]. In addition, Mullen and coworkers used the benzyl alcohol end-functionalized PF macroinitiator for synthesizing PF-b-PEO through the initiator of potassium naphthalenide [19]. Dai et al. employed the anionic polymerization of the vinyl end-functionalized P3HT macroinitiator to obtain P3HT-b-P2VP with different molecular weights [45]. Such block copolymers exhibited various morphologies of spheres, hexagonal closed packed cylinders, lamellae, and nanofibers by varying the rod–coil ratio.